KR101823758B1 - Synthetic leather having stain resistance and the preparation method thereof - Google Patents

Synthetic leather having stain resistance and the preparation method thereof Download PDF

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Publication number
KR101823758B1
KR101823758B1 KR1020160055320A KR20160055320A KR101823758B1 KR 101823758 B1 KR101823758 B1 KR 101823758B1 KR 1020160055320 A KR1020160055320 A KR 1020160055320A KR 20160055320 A KR20160055320 A KR 20160055320A KR 101823758 B1 KR101823758 B1 KR 101823758B1
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South Korea
Prior art keywords
layer
synthetic leather
polyurethane
coating
coating layer
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KR1020160055320A
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Korean (ko)
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KR20170125525A (en
Inventor
성낙현
Original Assignee
주식회사 비에스테크놀러지
주식회사 씨앤에스에프에이
성낙현
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Application filed by 주식회사 비에스테크놀러지, 주식회사 씨앤에스에프에이, 성낙현 filed Critical 주식회사 비에스테크놀러지
Priority to KR1020160055320A priority Critical patent/KR101823758B1/en
Priority to US15/179,242 priority patent/US9957662B2/en
Publication of KR20170125525A publication Critical patent/KR20170125525A/en
Application granted granted Critical
Publication of KR101823758B1 publication Critical patent/KR101823758B1/en
Priority to US15/922,629 priority patent/US20180202101A1/en

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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
    • D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
    • D06N3/0063—Inorganic compounding ingredients, e.g. metals, carbon fibres, Na2CO3, metal layers; Post-treatment with inorganic compounds
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
    • D06N3/0065—Organic pigments, e.g. dyes, brighteners
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/007—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by mechanical or physical treatments
    • D06N3/0077—Embossing; Pressing of the surface; Tumbling and crumbling; Cracking; Cooling; Heating, e.g. mirror finish
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
    • D06N3/128—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with silicon polymers
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/18—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with two layers of different macromolecular materials
    • D06N3/183—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with two layers of different macromolecular materials the layers are one next to the other
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
    • D06P5/003—Transfer printing
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2209/00—Properties of the materials
    • D06N2209/10—Properties of the materials having mechanical properties
    • D06N2209/103—Resistant to mechanical forces, e.g. shock, impact, puncture, flexion, shear, compression, tear
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2209/00—Properties of the materials
    • D06N2209/10—Properties of the materials having mechanical properties
    • D06N2209/106—Roughness, anti-slip, abrasiveness
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2209/00—Properties of the materials
    • D06N2209/14—Properties of the materials having chemical properties
    • D06N2209/142—Hydrophobic
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2209/00—Properties of the materials
    • D06N2209/16—Properties of the materials having other properties
    • D06N2209/1685—Wear resistance
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2211/00—Specially adapted uses
    • D06N2211/12—Decorative or sun protection articles
    • D06N2211/28—Artificial leather

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)

Abstract

(A) polyurethane synthetic leather; (b) a silane-based coating layer formed on the polyurethane synthetic leather to enhance bonding with the silicone coating layer; And (c) a silicone coating layer formed on the silane-based coating layer, and a method for producing the same.
The present invention not only shows the inherent texture and flexibility of natural leather, but also exhibits excellent water repellency, stain resistance, weatherability, and abrasion resistance due to the silane-based coating layer and silicone coating layer formed on the polyurethane synthetic leather.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a synthetic leather,

More particularly, the present invention relates to a synthetic leather having excellent stain resistance, water resistance, abrasion resistance and the like as well as showing smooth texture, flexibility and excellent surface effect of natural leather, ≪ / RTI >

In general, the fabric for interior decoration has a characteristic that once installed, it will not be removed for several years. If the fabric is contaminated with pollutants, it can not be removed individually, which is not good for cosmetics. These kinds of pollutants include ballpoint pens, markers, stationery, soil, dust, foreign matter or other organic matter. Also, when used in a commercial space such as a hospital, hotel, restaurant, etc., in the case of a textile fabric, a liquid stain or spill is impregnated on the back of the fabric, And the like.

On the other hand, polyurethane-coated fabric base is widely used as artificial leather. When such synthetic leather is used for commercial furniture, the stain resistance to the pollutants and the ease of cleaning are very important. In order to increase the stain resistance on the surface of the synthetic leather, the surface of the polyurethane coating layer is coated with a contaminant treatment agent such as a urethane base or a melamine base. In this case, (shiny) is increased, not the leather feeling, but the artificial feel like plastic. Further, in order to prevent the increase in shinyness, a small hardening agent may be added. In this case, however, the contamination effect is deteriorated, and the surface touch feeling becomes rather coarse and the merchantability is deteriorated.

In order to solve the above problems, a silicone synthetic leather product using silicone as a single surface coating layer has been put on the market, but it is difficult to generalize the product because of the high price of silicone raw material and difficulty in workability.

Disclosure of Invention Technical Problem [8] Accordingly, the present invention has been made in order to solve the above-mentioned problems, and it is an object of the present invention to provide a polyurethane synthetic leather composition which comprises a silane-based coating layer and a silicone coating layer successively formed thereon, And to provide a method for producing the same.

In order to achieve the above object, the present invention relates to (a) a polyurethane synthetic leather; (b) a silane-based coating layer formed on the polyurethane synthetic leather to enhance bonding with the silicone coating layer; And (c) a silicone coating layer formed on the silane-based coating layer.

In the present invention, the polyurethane synthetic leather (a) comprises: (a-1) a fabric layer constituting a base material of leather; And (a-2) a polyurethane coating layer formed on one side or both sides of the fabric layer.

In the present invention, the contaminated synthetic leather may further include (d) a print layer having a predetermined color or pattern between the polyurethane synthetic leather (a) and the silane-based coating layer (b).

In the present invention, the contaminated synthetic leather may further include a first adhesive layer (e) between the polyurethane synthetic leather (a) and the printing layer (d) to enhance the adhesive force therebetween.

In the present invention, the contaminated synthetic leather comprises (f) a second adhesive layer between the polyurethane synthetic leather (a) and the silane-based coating layer (b) And (g) a surface-strengthening layer formed on the second adhesive layer and enhancing the mechanical strength of the contaminated synthetic leather.

In the present invention, the silane-based coating layer (b) may be formed by crosslinking a modified alkylalkoxysilane having 1 to 10 carbon atoms. Here, the application amount of the silane-based coating layer (b) may be in the range of 20 to 30 g / m 2 .

In the present invention, the silicone coating layer (b) may be a linear siloxane; At least one cyclic siloxane; Siloxane-based copolymers; Silicone oil; And inorganic particles. Here, the application amount of the silicone coating layer (c) may be in the range of 20 to 50 g / m 2 .

In the present invention, the contaminated synthetic leather may be formed with an emboss pattern having a plurality of concave portions and convex portions on its surface.

According to another aspect of the present invention, there is provided a contaminated synthetic leather comprising: (i) preparing a polyurethane synthetic leather; (ii) coating a silane-based coating composition on one side or both sides of the polyurethane synthetic leather and then drying to form a silane-based coating layer; And (iii) coating a silicone coating composition on the silane-based coating layer and drying the silicone coating composition to form a silicone coating layer.

In the present invention, the polyurethane synthetic leather of step (i) may be a step of forming a polyurethane coating layer on one side or both sides of the fabric layer by dry or wet / dry processing.

In the present invention, the silane-based coating composition of the step (ii) comprises 6 to 16 parts by weight of a modified alkylalkoxysilane having 1 to 10 carbon atoms, based on 100 parts by weight of the composition; And a remaining amount of an organic solvent satisfying 100 parts by weight of the composition.

In the present invention, the silicone coating composition of the step (iii) may be a linear siloxane; At least one cyclic siloxane; Siloxane-based copolymers; Silicone oil; And a main agent in which an inorganic particle is blended with an organic solvent; And a liquid agent (two-liquid type) comprising a curing agent comprising a metal catalyst and an organic solvent.

In the present invention, the drying of step (iii) may be carried out at 60 to 75 ° C for 1 to 10 minutes; And a secondary aging step carried out at 70 to 90 DEG C for 24 to 30 hours.

The production method of the present invention is characterized in that, between steps (i) and (ii), (i-1) coating and drying a composition for forming a print layer on the polyurethane synthetic leather to form And forming a print layer.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view showing a process for producing a polyurethane synthetic leather according to a first embodiment of the present invention; ; And (i-3) arranging a print release paper having a transfer pattern on the semi-dried first adhesive layer in the state that the first adhesive layer is semi-dried, pressing the print release paper under a certain pressure and temperature to transfer the print layer And removing the release paper.

(I-4) a second adhesive coating composition is coated on one surface of the polyurethane synthetic leather and then dried to form a second adhesive layer ; And (i-5) disposing a surface reinforcing film on the semi-dried second adhesive layer.

In addition, the manufacturing method of the present invention may further include: (iv) embossing the surface of the dried silicon coating layer after the step (iii).

The contaminated synthetic leather fabric of the present invention not only exhibits excellent surface texture and flexibility, but also exhibits excellent stain resistance, water resistance and abrasion resistance due to sequentially formed polyurethane synthetic leather, silane-based coating layer and silicone coating layer.

Also, when used as a surface finishing material for furniture and interior decorations, it has excellent surface strength and is less prone to scratches, is not easily contaminated by pollution sources in everyday life, and can be easily removed even if it is contaminated.

1 is a cross-sectional view showing the construction of a contaminated synthetic leather according to an embodiment of the present invention.
2 is a sectional view showing the construction of a contaminated synthetic leather according to another embodiment of the present invention.
3 is a cross-sectional view showing the configuration of the contaminated synthetic leather according to another embodiment of the present invention.
4 is a cross-sectional view showing the configuration of the contaminated synthetic leather according to another embodiment of the present invention.
5 is a cross-sectional view showing the construction of a contaminated synthetic leather according to another embodiment of the present invention.
Figs. 6 to 9 are photographs showing pollution evaluation results of pollution sources (oil paints) of the contaminated synthetic leather of the present invention.
Figs. 10 to 12 are photographs showing the pollution resistance evaluation results of pollution source (mustard) of the contaminated synthetic leather of the present invention. Fig.
Figs. 13 to 14 are photographs showing the pollution evaluation results of the contamination source (ketchup) of the contaminated synthetic leather of the present invention.
15 to 16 are photographs showing the results of water repellency evaluation (coffee) of the contaminated synthetic leather of the present invention.
<Brief Description of Symbols>
100, 200, 300, 400, 500: Contaminated synthetic leather fabrics
110: Polyurethane synthetic leather 111: Fabric layer
112: polyurethane coating layer 120: first adhesive layer
130: print layer 140: second adhesive layer
150: surface strengthening layer 160: silane based coating layer
170: silicone coating layer

The construction of the present invention will now be described in detail with reference to the accompanying drawings.

Hereinafter, the expression such as &quot; B formed at the top (or bottom) of A &quot; or &quot; B formed at A &quot; B is attached to the upper or lower portion of A via an adhesive layer or an adhesive layer; Or the case where one or more separate layers are formed on the upper or lower part of A and the B is directly attached to the separate layer through an adhesive or an adhesive or the like.

In order to increase the stain resistance of polyurethane synthetic fabrics, that is, polyurethane coated fabrics coated with polyurethane, anti-contamination agents have been used. In this case, the contamination effect is partially increased, while the surface touch feeling is lowered, the surface gloss is increased, and the merchantability is lowered.

Silicone is also used alone because it is difficult to mix with other surface coating materials due to its low compatibility with other materials while having excellent stain resistance. However, when silicon is used as a 100% single coating material, costly silicon results in economical deterioration. In addition, due to the low chemical compatibility of silicon with other materials, it is impossible to exhibit the effects of fabrics and natural leather through various printing, making it impossible to create various surface effects.

Accordingly, the present invention solves the problems of a polyurethane-coated fabric substrate (e.g., polyurethane synthetic leather) and a silicone-coated fabric substrate (e.g., silicone synthetic leather) We want to secure the advantage of exertion simultaneously.

More specifically, the polyurethane resin exhibits polarity, while the silicone resin is non-polar and therefore chemically incompatible. For this reason, when a polyurethane resin and a silicone resin are mixed together as a component of a coating layer constituting synthetic leather, the basic properties including adhesive strength between the respective coating layers are remarkably lowered.

The present invention is characterized by introducing a silicone coating layer on the uppermost portion of the polyurethane synthetic leather and introducing a silane-based coating layer capable of physically and chemically bonding the polyurethane synthetic leather and the silicone coating layer into the intermediate layer .

Since the silane-based coating layer contains a siloxane bond (-Si-O-), the adhesion can be significantly increased due to high compatibility and affinity with the silicon coating layer in contact with the silane-based coating layer. Also, due to the polar moiety included in the silane-based coating layer, such as (meth) acryloyloxy group, the bonding force with the polyurethane coating layer exhibiting surface polarity can be increased. Accordingly, in the present invention, the polyurethane layer and the silicone coating layer are mixed as the main layer constituting the contaminant synthetic leather, and the environmentally friendly, low-cost polyurethane (polyurethane) ), And applying expensive silicon only to the surface layer, it is possible to maximize the merit of each of the polyurethane and silicon while improving the economical efficiency.

That is, the polyurethane coating layer can exhibit improved abrasion resistance, weather resistance, heat resistance, and cold resistance due to the polyurethane coating layer, and can exhibit excellent water resistance because the liquid does not penetrate. In addition, various surface effects can be produced through various printing on the polyurethane coating layer.

In addition, since the top coating layer is silicone-based, it is environmentally friendly and exhibits excellent resistance to pollution due to its low surface tension, while maintaining an excellent smooth surface texture and flexibility and a matte and waxy surface It is now possible to reproduce the touch of fine natural leather.

<Contaminated synthetic leather>

Hereinafter, each coating layer constituting the contaminated synthetic leather according to the present invention and its composition will be described. Here, the application amount of each coating layer constituting the contaminated synthetic leather of the present invention is based on the amount applied to 1 m 2 of the fabric, and the coating amount of each coating layer may be appropriately changed according to the weight of the fabric to be used.

1 to 5 are views schematically showing cross-sectional structures of a contaminated synthetic leather according to an embodiment of the present invention.

1, the contaminated synthetic leather 100 includes a polyurethane synthetic leather 110, a silane-based coating layer 120 and a silicone coating layer 130 on one or both surfaces of the polyurethane synthetic leather. ) Are sequentially formed.

In the present invention, the synthetic leather (110) may be a conventional polyurethane synthetic leather known in the art, and is not particularly limited.

Specifically, the polyurethane synthetic leather (110) comprises a fabric layer (111) constituting a base material of leather; And a polyurethane coating layer 112 formed on one side or both sides of the fabric layer.

The fabric layer 111 is used as a coating base of the polyurethane coating layer and serves as a backing for supporting the contaminated synthetic leather. The fabric layer 111 may be a woven or non-woven fabric known in the art, and is not particularly limited.

The woven or nonwoven fabric may be a woven fabric or a nonwoven fabric produced by using, for example, a synthetic resin fiber such as polyester fiber, viscose rayon fiber, polyamide fiber, polyurethane fiber, acrylic fiber, polyolefin fiber or cellulose fiber ; A woven fabric or nonwoven fabric made of cotton (for example, yarn made of cotton or cotton wool); Or a woven fabric or a nonwoven fabric produced by mixing the synthetic resin fibers and the cotton. Among these, woven fabrics made of a mixture of polyester fibers, viscose rayon fibers, polyamide fibers, polyester fibers and cotton or polyester fibers and viscose rayon are preferably used, but the present invention is not limited thereto. The polyester fabric is a fabric woven using polyester fibers that have been stretched to have little or no elongation. Such polyester fabrics have high tensile strength, low hygroscopicity, and excellent chemical resistance. In addition, stretch fabric materials such as spandex can be used.

The method for producing the woven or nonwoven fabric using the above-mentioned materials is not particularly limited, and may be manufactured by using, for example, a general paper making or weaving process. The thickness of the fabric layer 111 is not particularly limited, and may be in the range of 0.3 to 2 mm, for example.

The polyurethane coating layer 112 formed on the fabric layer 111 is a layer constituting the base of synthetic leather and shows a unique texture unique to leather while preventing the fabric layer 111 from being damaged And can exhibit improved abrasion resistance. Further, since the liquid does not penetrate, excellent water resistance can be exhibited.

The polyurethane coating layer 112 may be formed using a conventional polyurethane resin known in the art. For example, polyether polyurethane, polyester polyurethane, polycarbonate polyurethane, polyether ester polyurethane, polyether carbonate polyurethane, polycaprolactone polyurethane, hydrocarbon polyurethane, alicyclic polyurethane, aromatic polyurethane, May be used. The molecular weight of the polyurethane resin is not particularly limited.

The polyurethane coating layer 112 may be formed by a conventional method known in the art, for example, by dry processing or wet / dry processing.

For example, dry processing may be accomplished by a process of transfer coating and bonding the polyurethane resin onto the fabric layer using a release paper. The thickness of the polyurethane coating layer formed through such dry processing may be in the range of 0.1 to 0.3 mm, and the application amount of the polyurethane resin may be in the range of 50 to 200 g / m 2 on the solid basis.

Also, in the case of using wet / dry processing, a polyurethane coating composition by a wet process is coated and dried on one side or both sides of a fabric substrate (fabric layer), and then a surface coating layer (skin layer) is formed through the above- Polyurethane synthetic leather can be produced. In the polyurethane coating layer formed by such a wet / dry process, the application amount of the polyurethane resin may range from 150 to 500 g / m 2 based on solids, and preferably from 200 to 300 g / m 2 .

When the coating amount of the polyurethane coating layer by the dry or wet / dry processing falls within the above-mentioned range, not only the coating effect is excellent but also the drying speed is fast and the workability is good.

The polyurethane coating layer 120 may be transparent or pigmented in a pigmented form. The pigments may be any conventional organic and / or inorganic pigments known in the art.

In the present invention, a silane-based coating layer 160 is disposed between the polyurethane synthetic leather 110 and the silicone coating layer 170.

The silane-based coating layer 160 is disposed between the polyurethane synthetic leather 110 and the silicon layer 170 to facilitate bonding between the polyurethane synthetic leather 110 and the silicon layer 170, thereby significantly increasing the bonding strength. Due to the silane-based coating layer 160, the polyurethane layer which is the base layer of the synthetic leather and the silicon layer which is the surface layer can be mixed with each other in the present invention, so that various surface effects using the polyurethane are created, It is possible to exhibit stain resistance, excellent smooth surface texture, matte surface property, and waterproofness.

The silane-based coating layer 160 may be formed by using any conventional modified alkylalkoxysilane having 1 to 10 carbon atoms, which is known in the art. For example, a modified alkylalkoxysilane having an alkyl group having 1 to 10 carbon atoms and / or an alkoxy group and having an acryloyloxy group or a methacryloyloxy group at the terminal thereof can be used without limitation.

Non-limiting examples of usable modified alkylalkoxysilanes include acryloyloxypropyltrimethoxysilane, methacryloyloxypropyltrimethoxysilane, acryloyloxypropyltriethoxysilane, methacryloyloxy Propyltriethoxysilane, and the like. These may be used alone or in combination of two or more. Particularly, it is preferable to use 3- (acryloyloxy) propyltrimethoxysilane and / or 3- (methacryloyloxy) trimethoxysilane.

In addition to the above-described modified alkylalkoxysilanes, conventional alkylalkoxysilanes known in the art may further be used in the present invention. For example, a compound in which at least one alkyl group having 1 to 10 carbon atoms and at least one alkoxy group selected from methoxy, ethoxy and propoxy are directly bonded to a silicon atom, preferably monoalkyltrialkoxysilane .

Nonlimiting examples of alkylalkoxysilanes that can be used are methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, butyltrimethoxysilane, pentyltrimethoxysilane, hexyltrimethoxysilane, hexyl But are not limited to, trimethoxysilane, triethoxysilane, heptyltrimethoxysilane, heptyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, nonyltrimethoxysilane, nonyltriethoxysilane, decyltrimethoxysilane, Undecyltrimethoxysilane, undecyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, and the like. These may be used alone or in combination of two or more.

The silane-based coating layer 160 may be formed by using a modified alkylalkoxysilane as a base resin alone, or by cross-linking, further including conventional additives known in the art. For example, it is preferred that the modified alkylalkoxysilane includes a conventional crosslinking agent in the art.

In the present invention, the application amount of the silane-based coating layer 160 may range from 20 to 30 g / m 2 , preferably from 25 to 30 g / m 2 . When the applied amount of the silane-based coating layer is within the above-mentioned range, not only the adhesion effect between the polyurethane synthetic leather 110 and the silicone coating layer 170 is excellent but also the coating property is excellent and the workability is improved.

The silane-based coating layer 160 may be in the form of a transparent or pigmented colored layer, and preferably a transparent coating layer that can display various colors or patterns of the printing layer 140.

The silicone coating layer 170 of the present invention is formed on the silane-based coating layer 160, and exhibits excellent anti-fouling and abrasion resistance.

The silicone coating layer 170 may be formed by using a conventional silicone resin known in the art, or by mixing the silicone resin with other components.

According to one preferred embodiment of the present invention, the silicone coating layer 170 comprises (i) a linear siloxane; (ii) at least one cyclic siloxane; (iii) a siloxane-based copolymer; (iv) silicone oil; And (v) inorganic particles.

The linear siloxane may be a linear siloxane of a conventional linear structure known in the art. For example, linear polydimethylsiloxane may be used, and dimethylpolysiloxane may be preferably used.

The cyclic siloxane may be a siloxane containing an intramolecular ring. For example, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, or all of them may be used. The ratio of linear to cyclic siloxanes may range from 20 to 40: 80 to 60 by weight.

The siloxane-based copolymer is not particularly limited as long as at least one siloxane-based monomer is copolymerized. For example, a methylhydrosiloxane-dimethylsiloxane copolymer is preferable.

In addition, the silicone oil may be any of those conventionally known in the art, and may be in the form of an emulsion in which a dimethylpolysiloxane and water are mixed.

The inorganic particles may also include those conventionally known in the art. Using Non-limiting examples of inorganic particles can have such as silica (SiO 2), alumina (Al 2 O 3), SnO 2, MgO, CaO, titanium dioxide or mixtures thereof.

In the present invention, the application amount of the silicone coating layer 170 may be in the range of 20 to 50 g / m 2 , preferably in the range of 30 to 50 g / m 2 . When the application amount of the silicone coating layer falls within the above-mentioned range, not only the excellent stain resistance and the abrasion resistance are exhibited, but also the surface may have a matte and waxy effect.

The contaminated synthetic leather according to the present invention may further include a print layer having a predetermined color and / or pattern as required.

FIG. 2 schematically illustrates a cross-sectional structure of a contaminated synthetic leather 200 according to another embodiment of the present invention. The contaminated synthetic leather 200 includes a polyurethane synthetic leather 110, A silane-based coating layer 160, and a silicon coating layer 170 on a substrate (not shown).

Here, the position where the printing layer 130 is introduced is not particularly limited, and is preferably disposed between the polyurethane synthetic leather 110 and the silane-based coating layer 160.

In the present invention, the printed layer 130 is a layer that variously embodies the inherent color and / or pattern of the contaminated synthetic leather itself.

The color and / or the pattern of the print layer 130 are not particularly limited and may be appropriately adopted according to the purpose of use or the needs of the user. In one example, the printing layer may be in the form of a color containing conventional pigments in the art, or it may be of a shape that simultaneously contains a predetermined pattern and color.

The printing layer 130 may be formed using a conventional printing method known in the art and is not particularly limited thereto.

Non-limiting examples of printing methods that can be used in the present invention include screen printing, gravure printing, roto-gravure printing, flexographic printing, Offset Printing, Digital Printing, Transfer Printing, Rotary Printing, and the like. For example, the print layer 130 may be printed directly on the polyurethane synthetic leather using the printing method described above to achieve color or form a predetermined print pattern.

On the other hand, in the present invention, a print layer having a predetermined pattern can be formed by using a print release paper having a transfer pattern.

When the print layer is formed on the polyurethane synthetic leather by the transfer printing method as described above, the adhesive strength between the polyurethane synthetic leather and the print layer having the transfer pattern is lowered. Therefore, a first adhesive layer .

FIG. 3 schematically illustrates the cross-sectional structure of the contaminated synthetic leather 300 according to another embodiment of the present invention, wherein the contaminated synthetic leather 300 comprises a polyurethane synthetic leather 110, The first adhesive layer 120, the print layer 130, the silane-based coating layer 160, and the silicon coating layer 170 on the first adhesive layer 120.

The first adhesive layer 120 is formed on the polyurethane synthetic leather 110 and firmly bonds the synthetic leather and the printed layer 130. The first adhesive layer 120 is not particularly limited in terms of the constituent components thereof, the thickness and the application amount thereof, as long as the adhesion between the polyurethane synthetic leather 110 and the print layer 130 can be maintained.

In the present invention, the first adhesive layer 120 may be a conventional adhesive known in the art, and is preferably an urethane-based adhesive excellent in compatibility with a polyurethane coating layer, which is a main component of synthetic leather. As the urethane-based adhesive, a conventional two-pack type polyurethane adhesive known in the art may be used. Such a two-component adhesive may comprise a urethane-based main agent and a curing agent.

Also, the application amount of the first adhesive layer 120 may be in the range of 20 to 40 g / m 2 , preferably in the range of 30 to 40 g / m 2 . When the application amount of the first adhesive layer falls within the above-mentioned range, not only the adhesive property and the coating property are shown, but also the drying speed is fast and the workability is improved. In this case, the first adhesive layer 130 may be colored or colored in a transparent or pigmented state.

In the present invention, for example, the print layer 130 is formed by transfer printing. The first surface having the transfer pattern and the color in the both sides of the print paper is placed in contact with the first adhesive layer 120 After pressing and squeezing under constant temperature and pressure conditions and then removing the release paper, the pattern and color present in the printed release paper can be transferred onto the polyurethane synthetic leather.

The contaminated synthetic leather according to the present invention may further include a second adhesive layer and a surface strengthening layer as necessary.

FIG. 4 schematically illustrates a cross-sectional structure of a contaminated synthetic leather 400 according to another embodiment of the present invention, wherein the contaminated synthetic leather 400 comprises a polyurethane synthetic leather 110, A second adhesive layer 140, a surface strengthening layer 150, a silane-based coating layer 160, and a silicone coating layer 170 on the leather.

The position where the second adhesive layer 140 and the surface strengthening layer 150 are introduced is not particularly limited and preferably between the polyurethane synthetic leather 110 and the silane based coating layer 160, Is disposed between the printing layer 130 and the silane-based coating layer 160.

When the second adhesive layer 140 and the surface-strengthening layer 150 are disposed between the polyurethane synthetic leather 110 and the silane-based coating layer 160, the second adhesive layer 140 may be formed of polyurethane And is formed on the leather (110) to adhere the synthetic leather (110) and the surface strengthening layer (150). When the second adhesive layer 140 and the surface strengthening layer 150 are disposed between the print layer 130 and the silane-based coating layer 160, the second adhesive layer 140 is formed on the print layer 130 So as to firmly bond the polyurethane synthetic leather 110, the print layer 130 and the surface reinforcing layer 150 to each other.

In the present invention, the second adhesive layer 140 is not particularly limited in terms of the constituent components thereof, the thickness, and the application amount thereof, as long as the adhesive between the respective coating layers contacting each other can be maintained. For example, the second adhesive layer 140 may be composed of an adhesive component that is the same as or different from the first adhesive layer 120 described above. Preferably, the second adhesive layer 140 includes a urethane- .

The amount of the second adhesive layer 140 applied is not particularly limited, and may range, for example, from 20 to 40 g / m 2 , preferably from 30 to 40 g / m 2 . When the application amount of the second adhesive layer falls within the above-mentioned range, not only the adhesive property and the coating property are shown, but also the drying speed is fast and the workability is good. The second adhesive layer 140 may be transparent or pigmented in color.

In the present invention, the surface strengthening layer 150 disposed on the second adhesive layer 140 enhances the mechanical strength, surface strength and hardness of the contaminated synthetic leather of the present invention.

The surface strengthening layer 150 may be made of any conventional plastic film known in the art without limitation. For example, a film formed of PET (Polyethylene Terephthalate) or a PVC plastic material may be used, and it is preferably a PET film. The thickness of the surface strengthening layer 160 is not particularly limited, and may be in the range of, for example, 5 to 15 μm, and preferably in the range of 10 to 12 μm.

In addition to the above-described configuration, the present invention may further include a conventional water repellent layer or a protective layer known in the art.

The contaminated synthetic leather of the present invention including the above-described configuration may have the following five embodiments. However, the present invention is not limited to the following embodiments, and various modifications and applications are possible as needed.

1 is a cross-sectional view showing a first embodiment of a contaminated synthetic leather 100 according to the present invention.

Specifically, the contaminated synthetic leather (100) has a polyurethane synthetic leather (110) and a silane-based coating layer (160) and a silicone coating layer (170) sequentially formed on the first surface of the synthetic leather. Here, the polyurethane synthetic leather 110 includes a fabric layer 111, which is a base material of leather, and a polyurethane layer 112.

2 is a sectional view showing a second embodiment of the contaminated synthetic leather 200 according to the present invention.

Specifically, the contaminated synthetic leather (200) comprises a polyurethane synthetic leather (110), and a printed layer (130), a silane based coating layer (160), and a silicone coated layer (170) on the first side of the synthetic leather It is a sequentially formed structure.

3 is a cross-sectional view showing a second embodiment of the contaminated synthetic leather 300 according to the present invention.

Specifically, the contaminated synthetic leather (300) comprises a polyurethane synthetic leather (110), a first adhesive layer (120), a printed layer (130), a silane based coating layer (160) And a silicon coating layer 170 are sequentially formed.

4 is a cross-sectional view showing a third embodiment of the contaminated synthetic leather 400 according to the present invention.

Specifically, the contaminated synthetic leather (400) includes a polyurethane synthetic leather (110), a second adhesive layer (140), a surface strengthening layer (150), a silane based coating layer And a silicon coating layer 170 are sequentially formed.

5 is a cross-sectional view showing a fourth embodiment of the contaminated synthetic leather 500 according to the present invention.

Specifically, the contaminated synthetic leather (500) comprises a polyurethane synthetic leather (110), a first adhesive layer (120), a printed layer (130), a second adhesive layer A surface-strengthening layer 150, a silane-based coating layer 160, and a silicon coating layer 170 are sequentially formed.

In the present invention, a structure in which a silane-based coating layer 160 and a silicon coating layer 170 are sequentially formed on a polyurethane synthetic leather 110; Or a structure including the first adhesive layer 120, the print layer 130, the second adhesive layer 140, the surface-strengthening layer 150, and the like is further exemplified. However, it is not particularly limited, and it is also within the scope of the present invention that the number of coating layers constituting the antifouling synthetic leather and the order of lamination can be freely selected depending on the application. For example, the order of the above-described coating layers may be changed, or another surface layer may be introduced to have a multi-layer structure.

The contaminated synthetic leather (100) of the present invention may be embossed as needed to form an embossed pattern having a plurality of recesses and protrusions on its surface.

&Lt; Production method of contaminated synthetic leather >

Hereinafter, a method for producing a contaminated synthetic leather according to an embodiment of the present invention will be described. However, the present invention is not limited to the following production methods, and the steps of each process may be modified or optionally mixed as required.

In one preferred embodiment of the method for producing the contaminated synthetic leather, (i) preparing polyurethane synthetic leather (step S10); (ii) coating the silane-based coating composition on one side or both sides of the polyurethane synthetic leather and then drying to form a silane-based coating layer (step 'S20'); And (iii) coating a silicone coating composition on the silane-based coating layer and drying the coated silicone coating layer (step S30).

Between steps (i) and (ii), if necessary, (i-1) coating and drying a composition for forming a print layer on the polyurethane synthetic leather to form a print layer having a predetermined color or pattern (Step S11).

Between steps (i) and (ii), (i-2) a step of coating a first adhesive coating composition on one side of the polyurethane synthetic leather and drying to form a first adhesive layer S12-a step '); And (i-3) arranging a print release paper having a transfer pattern on the semi-dried first adhesive layer in the state that the first adhesive layer is semi-dried, pressing the print release paper under a certain pressure and temperature to transfer the print layer And removing the release paper (step S12-b).

Between the steps (i) and (ii), (i-4) a step of coating a second adhesive coating composition on one side of the polyurethane synthetic leather and drying to form a second adhesive layer Step S13 '); And (i-5) disposing the surface strengthening film on the second adhesive layer in the semi-dried state of the second adhesive layer (step S14).

In addition, after step (iii), (iv) embossing the surface of the dried silicon coating layer (step S40).

Hereinafter, the manufacturing method will be described separately for each process step as follows.

(1) Preparing polyurethane synthetic leather (hereinafter referred to as step S10).

In the step S10, a polyurethane synthetic leather used as a coating base of the contaminated synthetic leather is prepared.

In the present invention, the polyurethane synthetic leather can be obtained by using a conventional general-purpose polyurethane synthetic leather as it is or by forming a polyurethane coating layer on a fabric substrate (fabric layer) by conventional dry or wet / dry processing Can be used.

When the dry processing is used in step S10, a polyurethane synthetic leather can be produced by transcribing and bonding a polyurethane resin on a fabric layer using a release paper. The thickness of the polyurethane coating layer formed through such dry processing is 0.1 To be in the range 0.3 mm, and the coating amount of the polyurethane resin in the polyurethane coating layer is based on a solid content of 50 to 200 g / m 2 Lt; / RTI &gt;

Also, in the case of wet / dry processing, a polyurethane coating composition is coated and dried on one side or both sides of a fabric substrate (fabric layer) by a wet process, and then a surface coating layer is formed through the above- Can be prepared. In such wet / dry processing, it is preferred that the polyurethane coating composition comprises a polyurethane resin in the range of 150 to 500 g / m &lt; 2 &gt;

Here, the polyurethane coating composition is a liquid resin composition comprising a polyurethane resin and an organic solvent selected according to the material of the substrate, and may include a conventional curing agent in the art if necessary. In one example, the polyurethane resin is dispersed in an organic solvent and diluted to an appropriate concentration to prepare a coating composition. Examples of the polyurethane coating composition include 30 to 60 parts by weight of a polyurethane resin based on 100 parts by weight of the composition; And a remaining amount of an organic solvent satisfying 100 parts by weight of the composition, and preferably 35 to 45 parts by weight of a polyurethane resin. It may further comprise 5 to 15 parts by weight of pigment or other conventional additive.

The curing agent and the organic solvent may be any conventional ones known in the art. Non-limiting examples of usable solvents include ketone solvents such as methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), or acetone; Alcoholic solvents such as isopropyl alcohol (IPA) or n-hexanol; 1,2-dichlorobenzene, N-methylpyrrolidone (NMP) or N, N-dimethylformamide (DMF). If desired, the coating composition may contain a reinforcing filler or a bulking filler, such as colloidal silica, fumed silica; Colorants and pigments; Heat stabilizers, UV stabilizers and weather stabilizers; Flame retardants, thickeners, herbicides, preservatives, and the like.

The method of coating the polyurethane coating composition through the wet process in the step S10 is not particularly limited, and conventional coating methods known in the art can be applied. For example, it may be a bar coating method. The viscosity of the polyurethane coating composition may be in the range of 1,000 to 20,000 cps, but is not particularly limited thereto.

After the polyurethane coating layer is formed on the fabric layer by a dry process or a wet / dry process as described above, the formed polyurethane coating layer is exposed to air for a sufficient time to form a cured film. The drying time and conditions may be controlled within a conventional range, for example, room temperature or about 120 to 200 DEG C for 1 minute to 24 hours.

(2) Printing layer formation step

If necessary, in the present invention, the polyurethane synthetic leather or the print layer having a predetermined color or pattern can be formed on the first adhesive layer.

The printing layer formed in the step (2) may be in the form of a solid color containing pigments, or may be a pattern containing both a predetermined pattern and a color at the same time. Such a printing layer can be produced by a conventional method known in the art, and can be formed, for example, by the following two methods.

In the first embodiment of the above step (2), a color or a predetermined print pattern is formed by directly printing on a polyurethane synthetic leather using a conventional colorant composition (composition for forming a print layer) and a printing method Hereinafter referred to as step S11).

The colorant composition basically comprises a pigment and an additive, and may further comprise a binder as required. The pigments, additives, and binders may be used without limitation in the art, and their composition may be appropriately adjusted within the range known to those skilled in the art.

As the printing method of step S11, a conventional printing method known in the art can be used without limitation. Non-limiting examples thereof include but are not limited to screen printing, gravure printing, roto-gravure printing, flexographic printing, offset printing ), Digital printing, transfer printing, and rotary printing.

In the second embodiment of the above step (2), a predetermined pattern is formed by transferring the print release sheet having the transfer pattern on the first adhesive layer (hereinafter referred to as step S12).

In this case, when the first adhesive layer is completely dried, the adhesion of the first adhesive layer to the print release paper to be transferred may be deteriorated. Therefore, the first adhesive layer is preferably semi-dried so that the surface of the first adhesive layer is partially wet.

In a preferred example of the second embodiment of the step S12, (i-2) a first adhesive coating composition is coated on one side of the polyurethane synthetic leather and then dried to form a first adhesive layer ('S12-a (Step S12-b '), a print release sheet having a transfer pattern is disposed on the semi-dried first adhesive layer, and then the print release layer is removed by pressing the print release layer under a certain pressure and temperature (step S12-b) .

The first adhesive layer in the step S12-a may be used without limitation to a conventional adhesive component known in the art, and preferably a two-component urethane adhesive is used.

The two-component type urethane adhesive includes a polyurethane resin, a curing agent and an organic solvent. The curing agent may be 15 to 25 parts by weight based on 100 parts by weight of the polyurethane resin, and the organic solvent may be 65 To 80 parts by weight. Preferable examples of the two-component type urethane adhesive include a polyurethane resin; And 20 parts by weight of a curing agent and 70 parts by weight of an organic solvent (MEK) based on 100 parts by weight of the polyurethane resin. The application amount of the first adhesive may be in the range of 20 to 40 g / m 2 , preferably in the range of 30 to 40 g / m 2 .

In the step S12-a, the first adhesive may be coated by a conventional method known in the art, for example, by a known method such as roller printing. At this time, the drying condition of the first adhesive is not particularly limited, and for example, it may be carried out at 40 to 60 ° C for 1 to 10 minutes, preferably at 50 ° C for 2 minutes.

In addition, the print release sheet in step S12-b may be any conventional one known in the art. For example, a first surface having a predetermined transfer pattern and / or color and a second surface having a release layer have.

In step S12-b, the conditions for forming the printing layer through transfer are not particularly limited. For example, the printing layer is pressed under a pressure of 3 to 6 Kgf / m 2 and a temperature of 40 to 60 ° C for 1 to 30 minutes, And more preferably pressurized at a pressure of 5 kgf / m &lt; 2 &gt; and a temperature of 50 DEG C for 2 minutes.

The resulting product is first dried and then aged at 70 to 90 ° C for 5 to 30 hours to remove the release paper. After aging at such a temperature and time range, various patterns and colors on the release paper It is well transferred to urethane synthetic leather and can form a firm bond with polyurethane synthetic leather.

(3) a step of forming a second adhesive layer (hereinafter referred to as step S13).

If necessary, in the present invention, the second adhesive layer may be formed by coating and drying the second adhesive composition on the polyurethane synthetic leather or the printing layer.

At this time, the adhesive composition for forming the second adhesive and the coating method using the same may be applied in the same manner as in the step S12-a, but are not particularly limited.

(4) Step of forming a surface strengthening layer (hereinafter referred to as step S14).

If necessary, in the present invention, a surface strengthening film may be disposed on the second adhesive layer and then adhered to form a surface strengthening layer.

At this time, when the second adhesive layer is completely dried, the adhesion with the surface strengthening film may be deteriorated. Therefore, the surface of the second adhesive layer is desirably partially wetted.

Thereafter, the second adhesive layer and the surface reinforcing film are adhered to each other, dried first, and then subjected to a secondary aging process at 70 to 90 ° C for 5 to 30 hours. In this temperature and time range, the aging process is required to firmly bond the surface-reinforced layer and the polyurethane synthetic leather together.

(5) a step of forming a silane-based coating layer (hereinafter referred to as step S20).

In step S20, the silane-based coating composition is coated on the polyurethane synthetic leather and dried to form a silane-based coating layer.

At this time, steps S11 to S12 are performed; And / or S13 to S4 are carried out first, the silane-based coating composition is coated and dried on the printing layer or the surface-strengthening layer to form a silane-based coating layer.

The silane-based coating composition according to the present invention may be a liquid composition comprising a modified alkylalkoxysilane, an organic solvent, and a crosslinking agent selected depending on the material of the substrate.

As a preferable example of the silane-based coating composition in the step S20, 6 to 16 parts by weight of a modified alkylalkoxysilane having 1 to 10 carbon atoms, based on 100 parts by weight of the composition, And a remaining amount of an organic solvent satisfying 100 parts by weight of the composition, and may further include a conventional crosslinking agent known in the art if necessary.

The method of coating the silane-based coating composition in step S20 is not particularly limited, and conventional coating methods known in the art can be applied. Examples include spin coating, dip coating, solvent casting, slot die coating, spray coating, knife coting and gravure coating. gravure coating, and is preferably a gravure coating.

When the silane-based coating layer is formed by the gravure coating, the coating method, the coating condition, and the drying condition may be performed according to a conventional method known in the art. For example, a roll-to-roll press capable of gravure printing coating may be used.

The amount of the silane-based coating composition may be in the range of 20 to 30 g / m 2 , preferably 25 to 30 g / m 2 . The drying conditions of the silane-based coating composition are not particularly limited. For example, the drying may be carried out at 50 to 70 ° C for 1 to 10 minutes, preferably at 60 ° C for 2 to 5 minutes.

(6) a silicon coating layer forming step (hereinafter referred to as 'S30 step').

In step S30, a silicone coating composition is coated on the formed silane-based coating layer and then dried to form a silicone coating layer.

Silicone coating compositions that can be used in the present invention include (i) a linear siloxane; (ii) at least one cyclic siloxane; (iii) a siloxane-based copolymer; (iv) silicone oil; And (v) a main agent comprising inorganic particles in an organic solvent; And (vi) a curing agent comprising a metal catalyst and an organic solvent.

More specifically, a preferable example of the silicone coating composition includes 10 to 20 parts by weight of a linear siloxane; From 25 to 37 parts by weight of at least one cyclic siloxane; 2 to 5 parts by weight of a siloxane-based copolymer; 0.1 to 2 parts by weight of silicone oil; 1 to 5 parts by weight of inorganic particles; And 100 parts by weight of a main component; and 60 to 80 parts by weight of a metal catalyst; and 100 parts by weight of a curing agent, wherein the curing agent comprises a residual organic solvent satisfying 100 parts by weight of the curing agent. have.

The metal catalyst is a metal-containing curing catalyst. Examples of the metal catalyst include manganese acetylacetonate, iron acetylacetonate, dibutyltin dilaurate, dibutyltin diacetate, May be at least one selected from the group consisting of copper (II) acetylacetonate (Cupper (II) acetylacetonate), zinc octanate, zirconium naphthalate and tetrabutyl titanate, preferably dibutyltin dilaurate have.

The viscosity of the uniformly mixed silicone coating composition is not particularly limited, but is preferably 200 to 1,000 cps / 25 占 폚.

The method of coating the silicone coating composition in step S30 is not particularly limited, and conventional coating methods known in the art can be applied. Examples include spin coating, dip coating, solvent casting, slot die coating, spray coating, knife coting, and gravure coating. gravure coating, and is preferably a gravure coating.

When the silicone coating layer is formed by the gravure coating, the coating method, the coating condition, the drying condition, and the like can be performed according to a conventional method known in the art. For example, a roll-to-roll press capable of gravure printing coating may be used.

The application amount of the silicone coating composition may range from 20 to 50 g / m 2 , preferably from 30 to 50 g / m 2 .

The applied silicone coating layer is subjected to a drying process. The drying condition is not particularly limited. For example, the silicone coating layer is first dried at 60 to 75 ° C for 1 to 10 minutes, preferably at 70 ° C for 2 to 5 minutes, It is preferable that the dried silicon coating layer is subjected to a second aging step at 70 to 90 ° C for 24 to 30 hours.

(7) emboss processing step (hereinafter referred to as step S40).

If necessary, the present invention may further include embossing the surface of the dried silicon coating layer.

At this time, embossing conditions are not particularly limited and may be performed according to a conventional method known in the art.

The contaminated synthetic leather of the present invention manufactured as described above can be applied to various indoor or outdoor interior products. The interior product can be applied to all products to which the stain resistant and waterproof synthetic leather of the present invention can be introduced, and examples thereof include wallpaper, furniture, flooring, interior materials, exterior materials, surface materials, wood, have.

Hereinafter, the present invention will be described in detail with reference to examples. However, these examples are for illustrating the present invention specifically, and the scope of the present invention is not limited to these examples.

Example 1. Preparation of contaminated synthetic leather (1)

A polyurethane coating composition (viscosity: 5000-7000 cps) comprising a polyurethane resin having a molecular weight of 20,000 to 200,000 and an organic solvent mixed with dimethylformamide (DMF) and methyl ethyl ketone (MEK) Criterion 100 g / m &lt; 2 & gt ;. And dried at 140-180 [deg.] C for 1-5 minutes to form a polyurethane coating layer. Here, the polyurethane coating composition of the dry process was prepared by mixing 40% by weight of a polyurethane resin (polyurethane solid content 30%, solvent 70%); 50% by weight of solvent (DMF 100%); And 10% by weight of other components such as pigments (solid content 50%, solvent 50%).

Then, the polyurethane bimodal adhesive composition was coated on the polyurethane synthetic leather (fabric having the polyurethane coating layer formed thereon) in a range of 40 g / m 2 , coated, and then dried. The composition and content of the first adhesive composition are shown in Table 1 below.

After the first adhesive composition was semi-dried, a print release paper having a transfer pattern was placed, and the pressure was applied for 2 minutes under a pressure of 5 kgf / m 2 and a temperature of 50 캜 to transfer the print layer having the transfer pattern , And the transferred product was aged at 70 to 90 ° C for 5 to 30 hours, and then the release paper was removed.

On the printing layer of the polyurethane synthetic leather, a polyurethane two-pack type adhesive composition was applied in a range of 40 g / m 2 , coated, and then dried. The composition and content of the second adhesive composition are shown in Table 1 below.

After the second adhesive composition was semi-dried, a PET film (one-piece, uncoated) was placed as the surface strengthening layer, and then pressed at a pressure of 6.5 kgf / m 2 and a temperature of 50 ° C for 2 minutes.

The silane-based coating composition was gravure coated on the surface-reinforced layer of the polyurethane synthetic leather, dried, and applied in a range of 25 g / m 2 . The composition and content of the silane-based coating composition are shown in Table 1 below.

Next, the silicone coating composition was gravure coated on the coated silane-based coating layer, dried and applied at a coverage of 40 g / m &lt; 2 &gt;, and then subjected to embossing to produce contaminant synthetic leather. The structure of the final fabricated contaminated synthetic leather is shown in Fig.

Example 2. Preparation of contaminated synthetic leather (2)

Except that the silane-based coating layer and the silicon coating layer were sequentially formed on the polyurethane synthetic leather without performing the steps of forming the first adhesive layer, the print layer, the second adhesive layer, and the surface- 1, a solid type of contaminated synthetic leather 2 was produced. The structure of the final fabricated contaminated synthetic leather is shown in Fig.

Example 3: Preparation of contaminated synthetic leather (3)

Except that the first adhesive layer, the printing layer, the silane-based coating layer and the silicon coating layer were formed on the polyurethane synthetic leather without performing the step of forming the second adhesive layer and the surface-reinforced layer. The same procedure was carried out to prepare the contaminated synthetic leather (3). The structure of the final fabricated contaminated synthetic leather is shown in Fig.

Example 4. Preparation of contaminated synthetic leather (4)

Except that the second adhesive layer, the surface reinforcing layer, the silane-based coating layer and the silicon coating layer were formed on the polyurethane synthetic leather without performing the steps of forming the first adhesive layer and the printing layer. The same procedure was repeated to produce the contaminated synthetic leather (4). The structure of the final fabricated contaminated synthetic leather is shown in Fig.

Example 5. Preparation of contaminated synthetic leather (5)

A printing layer, a silane-based coating layer and a silicone coating layer are formed on a polyurethane synthetic leather, respectively, without forming the first adhesive layer, the second adhesive layer and the surface-reinforced layer, (5) was produced in the same manner as in Example 1, except that a printed layer was formed by directly coating and drying on polyurethane synthetic leather. The structure of the final fabricated contaminated synthetic leather is shown in Fig.

sequence of the work Composition content
(wt%) Coating amount based on solid content
(g / m 2 ) Working condition
(Hour / C) Coating method One Polyurethane coating Polyurethane resin 40 100 140-180 DEG C, 1-5 minutes Release paper knife coating Solvents and other ingredients 60 2 The first adhesive coating The liquid type polyurethane adhesive composition 40 Chamber temperature 50 캜, 2 minutes Gravure knife coating 3 Print Release Press pressure 5 kgf / cm 2 4 Second adhesive coating The liquid type polyurethane adhesive composition 40 50 캜, 2 minutes Gravure knife coating 5 Surface strengthening layer 6 Silane system
coating Ethyl acetate 75 ~ 85 25 50 캜, 2 minutes Gravure coating Methyl alcohol 1-3 Modified methyltrimethoxysilane 6 ~ 16 7 silicon
coating Octamethylcyclo
Tetrasiloxane 0.2 to 1.2 40 Drying: 70 ° C, 2 minutes Gravure coating Decamethylcyclo
Tetrasiloxane 25 to 35 Polydimethylsiloxane 10-20 Siloxane copolymer 2 to 3 Aging: aging room 80 캜, 48 hours Silicone oil 0.2 to 1.2 Silica 1-2 Methylcyclohexane 40 to 50 Dibutyl tin dilaurate 65 ~ 75 Isopropyl alcohol 20 ~ 30 8 Emboss - The amount of coating is based on the amount applied to 1 m 2 of fabric and may vary depending on the fabric weight.

Constituent Manufacturer / model name
(CAS No.) Manufacturer / model name One Polyurethane
coating Polyurethane resin ISU-409 Sun Solvent (DMF) 68-12-2 Daewon Hwaseong Solvent (MEK) 78-93-3 Daewon Hwaseong 2 The first adhesive
coating The liquid polyurethane
Adhesive composition 6200 Jinsan Chemical 3 The second adhesive
coating The liquid polyurethane
Adhesive composition 6200 Jinsan Chemical 4 Silane-based coating Ethyl acetate 141-78-6 Eisse F Methyl alcohol 67-56-1 Modified methyltrimethoxysilane 2530-85-0 5 Silicone coating
(subject) Octamethylcyclotetrasiloxane 556-67-2 Eisse F Decamethylcyclotetrisiloxane 541-02-6 Polydimethylsiloxane 70131-67-8 Siloxane copolymer
(Methylhydrosiloxane-dimethylsiloxane copolymer) 68037-59-2 Silicone oil
(dimethylsiloxane / water emulsion) 63148-62-9 Silica 7631-86-9 Methylcyclohexane 108-87-2 Silicone coating
(Hardener) Dibutyl tin dilaurate 77-58-7 Isopropyl alcohol 67-63-0

Experimental Example 1. Evaluation of physical properties of contaminated synthetic leather

(1) Evaluation of pollution in the interior

The contamination resistance evaluation was carried out using the contaminated synthetic leather produced in Examples 1 and 2. [

The evaluation method is repeated 50 times using the same pollutant source to visually check the degree of contamination of each. In this case, oiled ballpoint pen, mustard, and ketchup were used as pollutants.

Experimental results show that the oil-based ballpoint pens in the contaminated synthetic leather of Examples 1 and 2 are easily erased by an eraser and a fabric / paper towel without using a special cleaner (see FIGS. 6 to 9).

Also in case of mustard or ketchup, the contaminated synthetic leather of Examples 1 and 2 was also cleaned without any contamination left by the fabric / paper towel without using a separate cleaner (see Figs. 10 to 14).

Therefore, it was found that the contaminated synthetic leather of the present invention has a remarkably excellent stain resistance effect as compared with the control group.

(2) Evaluation of water repellency

Water repellency evaluation was performed using the contaminated synthetic leather prepared in Examples 1 and 2.

The above evaluation method is to evaluate the shape and the degree of absorption of the dropped coffee by visually checking after dropping it on synthetic leather using coffee. At this time, coffee was used as the water repellency evaluation material of the present invention since it is a substance having better penetration effect than water.

As a result of the experiment, the coffee dropped on the contaminated synthetic leather of Examples 1 and 2 remained in shape over time and was not absorbed into the synthetic leather. Therefore, it was found that the contaminated synthetic leather of the present invention had an excellent water repellency effect (see Figs. 15 to 16).

(3) Evaluation of abrasion resistance (friction fastness)

The anti-fouling synthetic leather of Examples 1 and 2 was tested according to ASTM D 4157-13, " Standard Test Method for Abrasion Resistance of Textile Fabrics (Oscillatory Cylinder Method) ".

Generally, if the wear resistance test result is over 30,000 rubs, it is usually classified as heavy duty, and if it exceeds 50,000 rubs, it is considered to be commercially suitable.

The antifouling synthetic leather of the transfer printing of Example 1 of the present invention exceeded 200,000 rubs. Also, the stain resistant synthetic leather of the solid type product of Example 2 exceeded 1,000,000 rubs (see Table 3).

Test results Example 1 Passed 200,000 Cycles Example 2 Passed 1,000,000 Cycles Abradant: # 10 cotton duck;
tension: 4 lb
load: 3 lb

(4) Evaluation of my cleaner

Various cleaners are used for commercial and hospital use, and the durability of these cleaners is a very important requirement of the product.

Ten AATCC tests were conducted on 10 cleaners that are mainly used as hospital cleaners. At this time, evaluation criteria and evaluation results of the inner cleaner characteristics are shown in Tables 4 to 5, respectively.

As a result of the test, the contaminated synthetic leather of Examples 1 and 2 showed excellent results (see Table 5).

AATCC Test 130 (Stain Release) Class 5 (ISO 5) No color change (best my cleaner characteristic) 4th grade (ISO 4) Slight color change occurred (slight) Class 3 (ISO 3) Partial color change occurrence (moderate) Class 2 (ISO 2) Significant color changes occur (considerable) Class 1 (ISO 1) Excessive color change (excessive)

Hospital Cleaner Color change rating observe Colorex Germicidal Wipes 5 No change PDI Sani Super Wipes 5 No change PDI Sani Plus Wipes 5 No change PDI Sani Bleach 5 No change Johnson Diversey Virex II 256 5 No change Virex TB 5 No change 3M HB Quat 5 No change WexCide 128 5 No change Accel TB 5 No change Amphyl 5 No change

Claims (18)

(a) Polyurethane synthetic leather;
(b) a silane-based coating layer formed on the polyurethane synthetic leather to enhance bonding with the silicone coating layer; And
(c) a silicon coating layer formed on the silane-
Resistant synthetic leather. The method according to claim 1,
The polyurethane synthetic leather (a)
(a-1) a fabric layer constituting a base material of a leather; And
(a-2) a polyurethane coating layer formed on one side or both sides of the fabric layer
Resistant synthetic leather. The method according to claim 1,
Wherein the contaminated synthetic leather further comprises (d) a printing layer having a predetermined color or pattern between the polyurethane synthetic leather (a) and the silane-based coating layer (b). The method of claim 3,
The contaminated synthetic leather further comprises (e) a first adhesive layer between the polyurethane synthetic leather (a) and the printed layer (d) to enhance the adhesive strength. The method according to claim 1,
The contaminated synthetic leather is provided between the polyurethane synthetic leather (a) and the silane-based coating layer (b)
(f) a second adhesive layer; And
(g) a surface-strengthening layer formed on the second adhesive layer, the surface-strengthening layer enhancing the mechanical strength of the synthetic leather. The method according to claim 1,
Wherein the silane-based coating layer (b) is formed by cross-linking a modified alkylalkoxysilane having 1 to 10 carbon atoms. The method according to claim 1,
Wherein the amount of the silane-based coating layer (b) applied is in the range of 20 to 30 g / m 2 . The method according to claim 1,
The silicone coating layer (c) may be a linear siloxane; At least one cyclic siloxane; Siloxane-based copolymers; Silicone oil; And an inorganic particle. The method according to claim 1,
Wherein the coating amount of the silicone coating layer (c) is in the range of 20 to 50 g / m &lt; 2 &gt;. The method according to claim 1,
Wherein an embossed pattern having a plurality of concave portions and convex portions on its surface is formed. (i) preparing a polyurethane synthetic leather;
(ii) coating a silane-based coating composition on one side or both sides of the polyurethane synthetic leather and then drying to form a silane-based coating layer; And
(iii) coating a silicon coating composition on the silane-based coating layer and then drying to form a silicone coating layer
The method of manufacturing the contaminated synthetic leather according to claim 1, 12. The method of claim 11,
The silane-based coating composition of the step (ii) comprises 6 to 16 parts by weight of a modified alkylalkoxysilane having 1 to 10 carbon atoms, based on 100 parts by weight of the composition; And a residual amount of an organic solvent satisfying 100 parts by weight of the composition. 12. The method of claim 11,
Wherein the silicone coating composition of step (iii) is selected from the group consisting of linear siloxanes; At least one cyclic siloxane; Siloxane-based copolymers; Silicone oil; And a main agent in which an inorganic particle is blended with an organic solvent; And
(Two-part type) comprising a curing agent comprising a metal catalyst and an organic solvent. 12. The method of claim 11,
In step (iii) above, drying
A primary drying step carried out at 60 to 75 ° C for 1 to 10 minutes; And
And a second aging step carried out at 70 to 90 DEG C for 24 to 30 hours. 12. The method of claim 11,
The manufacturing method is characterized in that between steps (i) and (ii)
(i-1) a step of coating and drying a composition for forming a print layer on the polyurethane synthetic leather to form a print layer having a predetermined color or pattern. Way. 12. The method of claim 11,
The manufacturing method is characterized in that between steps (i) and (ii)
(i-2) coating a first adhesive coating composition on one side of the polyurethane synthetic leather and then drying to form a first adhesive layer; And
(i-3) In the state that the first adhesive layer is semi-dried, the release paper on which the print layer having the transfer pattern is formed is placed on the semi-dried first adhesive layer, Step of transferring and removing the release paper
Wherein the method further comprises the step of: 12. The method of claim 11,
The manufacturing method is characterized in that between steps (i) and (ii)
(i-4) coating a second adhesive coating composition on one side of the polyurethane synthetic leather and then drying to form a second adhesive layer; And
(i-5) placing the surface strengthening film on the semi-dried second adhesive layer
Wherein the method further comprises the step of: 12. The method of claim 11,
The manufacturing method may further include, after the step (iii)
(iv) embossing the surface of the dried silicone coating layer.
KR1020160055320A 2016-05-04 2016-05-04 Synthetic leather having stain resistance and the preparation method thereof KR101823758B1 (en)

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